CN103923237B - Catalyst component for olefin polymerization and application thereof - Google Patents

Catalyst component for olefin polymerization and application thereof Download PDF

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CN103923237B
CN103923237B CN201410163260.0A CN201410163260A CN103923237B CN 103923237 B CN103923237 B CN 103923237B CN 201410163260 A CN201410163260 A CN 201410163260A CN 103923237 B CN103923237 B CN 103923237B
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methyl
formic acid
compound
ester
hydrogen
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CN103923237A (en
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王志武
李树行
李华姝
张军伟
李树宾
代金松
马庆利
陈颢
李利革
白伟
雷凤瑶
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Beijing Li Hezhixin Science and Technology Ltd.
Li Zhixin New Materials Technology Co., Ltd.
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/647—Catalysts containing a specific non-metal or metal-free compound
    • C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
    • C08F4/6494—Catalysts containing a specific non-metal or metal-free compound organic containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes

Abstract

The invention provides a solid catalyst component for olefin polymerization, which comprises Mg, Ti, halogen and electron donor, wherein the electron donor is selected from at least one of cyclosubstituted ether acid ester compounds disclosed as general formula (I). The invention also provides a catalyst containing the solid catalyst component and application of the catalyst in olefin polymerization reaction, particularly application in propylene polymerization reaction. The specific cyclosubstituted-structure compounds contained in the solid catalyst component have a steric effect, can fix the spatial configuration of the ether and acid ester functional groups, and have active functions on participating in the formation of the catalyst activity center and enhancing the stereospecificity of the catalyst. The solid catalyst component has excellent activity, and the prepared polymer has high degree of isotacticity.

Description

Catalytic component for olefinic polymerization and its application
Technical field
The present invention relates to a kind of be used for ch2The ingredient of solid catalyst of=chr olefinic polymerization, wherein r are hydrogen or contain 1-12 The hydrocarbyl group of individual carbon atom, it is more particularly related to the ring containing at least one specific type replaces ether acid esterification The ingredient of solid catalyst of compound, the catalyst containing this ingredient of solid catalyst and this catalyst are in olefinic polyreaction Application, the application especially in propylene polymerization.
Background technology
Electron donor compound can change the property in olefinic polymerization Ziegler-Natta catalyst active center most possibly Matter, thus farthest changing the performance of catalyst, the research of therefore efficient Ziegler-Natta catalyst is in some sense Say the research being exactly to seek more preferable electron donor.Both at home and abroad the research of internal electron donor is focused primarily upon traditional at present Fatty acid ester and aromatic esters compound；Two ethers (such as ep0361493, ep0728724) and succinate compound is (for example Wo9856834, wo0063261, wo03022894) compound；And diol-lipid (such as cn1580033, cn1580034, Cn1580035) compound etc..But above-claimed cpd as catalyst component for olefin polymerization electron donor in actual applications All there is certain problem, the molecular weight distribution of the catalyst system resulting polymers such as prepared using diether compound is relatively Narrow, and the polymeric articles molecular weight distribution of succinate compound catalyst system is wider, the activity of diol-lipid catalyst system and catalyzing is past Toward not as two ethers systems ideals.In order that catalyst can obtain the combination property of more balance, develop various new changes Compound simultaneously is applied to prepare Ziegler-Natta catalyst.
It is to seek there is outstanding combination property electron donor compound that multiple functional groups are incorporated in a compound structure A general orientation, the existing many at present reports with regard to preparing and applying polyfunctional compound, such as exploitation ketone-ether combine (wo2010144079), ketone -ester combine (wo2005097841), ether-ester combine (wo2005123784, wo2012087522, Wo2012087527 new internal electron donor), its main purpose is intended to comprehensively utilize the advantage of variant functional group
But using above-claimed cpd preparation activity when for olefinic polymerization for the Ziegler-Natta catalyst component/ The balance of isotacticity and unsatisfactory it is therefore desirable to be researched and developed further to it.
Content of the invention
It is an object of the invention to provide a kind of be used for ch2The ingredient of solid catalyst of=chr olefinic polyreaction.
Another object of the present invention is to providing the preparation method of this ingredient of solid catalyst.
It is still another object of the present invention to provide this ingredient of solid catalyst is in ch2Prepared by=chr olefin polymerization catalysis In application.
In order to realize the purpose of the present invention, the present invention provides a kind of ingredient of solid catalyst (alkene for olefinic polymerization ch2=chr, wherein r are hydrogen or the hydrocarbyl group containing 1-12 carbon atom), it comprises mg, ti, halogen and a kind of electron donor, This electron donor is selected from least one ring replacement ether acid ester compounds of following formulas ():
Wherein, a, b, c, d and e are carbon atom or the hetero atom in n, o and s；W, x, y, z and m are 0,1 or 2；Bar Part is
When n is equal to 0:
Ix) b is nitrogen-atoms, and a, c and d are carbon atoms, and x is 1, and w, y and z are 2；Or
X) c is nitrogen-atoms, and a, b and d are carbon atoms, and y is 1, and w, x and z are 2；Or
Xi) c is oxygen atom, and a, b and d are carbon atoms, and y is 0, and w, x and z are 2；Or
Xii) a and c is oxygen atom, w and y is 0, x and z is 2；Or
Xiii) b is oxygen atom, and a, c and d are carbon atoms, and x is 0, and w, y and z are 2；Or
Xiv) a, b, c and d are carbon atom and pass through singly bound each other, and w, x, y and z are 2；Or
Xv) a, b, c and d are carbon atom, are bonded by double bond between b and c, x and y is 1, w and z is 2；Or
Xvi) a, b, c and d are carbon atom, are bonded by double bond respectively between a and d, b and c, and w, x, y and z are 1；
When n is equal to 1:
X) d is nitrogen-atoms, and a, b, c and e are carbon atom, and z is 1, and w, x, y and m are 2；Or
Xi) e is nitrogen-atoms, and a, b, c and d are carbon atom, and m is 1, and w, x, y and z are 2；Or
Xii) e is oxygen atom, and a, b, c and d are carbon atom, and m is 0, and w, x, y and z are 2；Or
Xiii) c and d is oxygen atom, and a, b and e are carbon atom, y and z is 0, and w, x and m are 2；Or
Xiv) d is oxygen atom, and a, b, c and e are carbon atom, and z is 0, and w, x, y and m are 2；Or
Xv) b is oxygen atom, and a, c, d and e are carbon atom, and x is 0, and w, y, z and m are 2；
Xvi) a, b, c, d and e are carbon atom, and w, x, y, z and m are 2；
Xvii) a, b, c, d and e are carbon atom, are bonded by double bond between b and c, x and y is 1, and w, z and m are 2；Or
Xviii) a, b, c, d and e are carbon atom, are bonded by double bond respectively between a and d, b and c, and w, x, y and z are 1, M is 2；
When n is equal to 2,
A and b is carbon atom, w and x is carbon atom, sulphur atom, oxygen atom or nitrogen-atoms for 2, c and d, y and z is 2 or 0, e Represent two carbon atoms being mutually bonded by singly-bound or double bond, when e is to be bonded by double bond, m is equal to 1, and ought above-mentioned be During by singly bound, m is equal to 2；
r1And r4For c that is identical or differing1-c20Alkyl, such as c1-c20Straight or branched alkyl, alkenyl, c3-c20 Cycloalkyl, c6-c20Aryl, c7-c20Alkaryl and c7-c20Aralkyl；Identical or different r2、r3、r5-r9It is hydrogen atom, halogen Atom, oxygen atom, sulphur atom and c1-c20Alkyl, such as c1-c20Straight or branched alkyl, c3-c20Cycloalkyl, c6-c20Virtue Base, c7-c20Alkaryl and c7-c20Aralkyl；
Above-mentioned r1-r9Arbitrarily comprise one or several r atoms as carbon atom or hydrogen atom or both substituents, r Atom is hetero atom, the c of straight or branched1-c20Alkyl, c3-c20Cycloalkyl, c6-c20Aryl, c7-c20Alkaryl and c7-c20Virtue Alkyl；Wherein r1-r9Any two group can be mutually bonded the one or more volutions of generation, condensed cyclic structure.
Instantiation including the compound in formula () is:
Instantiation including the compound in formula () is:
Five-membered ring ether acid ester compounds: ethyl 1- (1,1- ethylene dioxy ethyl) Pentamethylene. -1- formic acid esters；Ethyl 2- (1- Methoxy cyclopentane) -2- 2-Methoxyacetic acid ester；Methyl 1- (methoxyl methyl) cyclopentane-carboxylic acid ester；1- (benzyloxymethyl) cyclohexyl Methyl formate；1- (4,4,6- trimethyls-[1,3] azepine pyrans -2- base)-cyclopenta Ethyl formate；2- chloro- methoxyethyl -1- Cyclopenta methyl formate；Two ＜ methyl cyclohexanecarboxylaand ＞ dimethyl cellosolves；2- benzyloxy-(1,1- ethylene dioxy ethyl)-cyclopenta Ethyl formate；And methyl isophthalic acid-methoxyl group bicyclo- ＜ 2.2.2 ＞ octyl- 8- alkene -2,6- dicarboxylic acid methyl ester；1- methoxyl group earrings ＜ 2.2.2 ＞ Octyl- 9- alkane, trimethyl -1- methoxyl group earrings ＜ 2.2.1 ＞ heptane -2,6,10- front three acid esters；1- methoxyl group -1- cyclopentane-carboxylic acid Ethoxycarbonyl -3 phenyl-acryloyl；2- benzyloxymethyl -2- carbethoxyl group -1- (Pentamethylene oxide. -2- oxygen) oxygen Pentamethylene.；2- benzyloxy- 2- carbethoxyl group-cyclopentanol；Methyl 1- (1- methoxyethyl) cyclopentanecarboxylic acid ester；2- methyl -2 (1- cyclopenta Ethyl formate -1- Base) -4- methylene -1,3- oxopropan；Methyl-(3,4- dihydro -1 hydrogen-different pyrans -1- base) cyclopenta formic acid esters；Ethyl 1- (methoxyl methyl) cyclopentane-carboxylic acid ester；Methyl isophthalic acid-(ethoxymethyl) cyclopentane-carboxylic acid ester；2- benzyloxymethyl -1- Ketocyclopentane-first Acetoacetic ester；1- benzyloxymethyl-nafoxidine -2- methyl formate；Methyl-hexahydro -2,2,7- trimethyl -6- oxo [1,3] dioxies [5,4-b] pyrroles -4a- formic acid esters；Methyl -2- benzyloxymethyl -5- carbonyl nafoxidine -2- formic acid esters；Methyl 1- (4- chlorine Benzene) -3- (methoxyl methyl) -4,5- dicarbapentaborane pyrroles's -3- formic acid esters；3- methoxyl methyl-nafoxidine -3- methyl formate；Uncle 1- Butoxycarbonylmethyl -3- methoxyl methyl-nafoxidine -3- formic acid esters；1- benzyl -3- methoxyl methyl-nafoxidine -3- formic acid first Ester；2- ethoxymethyl-nafoxidine -1,2- dioctyl phthalate 1- tert-butyl ester 2- methyl ester；2- isopropoxymethyl-nafoxidine -1,2- bis- Formic acid 1- tert-butyl ester 2- ethyl ester；Methyl 3- methoxyl methyl -1- (3- tolyl) -4,5- dicarbapentaborane nafoxidine -3- formic acid esters；First Base 3- methoxyl methyl -1- (4- fluorophenyl) -4,5- dicarbapentaborane nafoxidine -3- formic acid esters；Methyl 3- methoxyl methyl -1- (4- bromine Phenyl) -4,5- dicarbapentaborane nafoxidine -3- formic acid esters；Methyl 1- (4- hydroxy phenyl) -3- methoxyl methyl -4,5- dicarbapentaborane four Hydrogen pyrroles's -3- formic acid esters；Ethyl 3- ethoxymethyl -1- phenyl -4,5- dicarbapentaborane nafoxidine -3- carboxylate；Ethyl 3- ethoxy Methyl isophthalic acid-(3 tolyl) -4,5- dicarbapentaborane nafoxidine -3- carboxylate；3- methoxyl methyl -2- carbonyl-oxolane -3- first Acetoacetic ester；3- isopropoxymethyl -2- carbonyl-oxolane -3- Ethyl formate；1- (4,4,6- trimethyls-[1,3] oxazines -2- Base)-cyclopenta Ethyl formate；Methyl -3- ethyl -2- ＜ (2- trimethyl silicane ethyoxyl) methoxyl methyl ＞-Isosorbide-5-Nitrae-dioxo spiro ＜ 4.4 ＞ nonane -2- formic acid esters；Methyl 5- oxygen-phenyl -2- deoxidation -4- methoxycarbonyl group-d- furan pentose glycosides；2- benzyloxymethyl -3- (2- methoxyvinyl) -2- methoxycarbonyl group-Isosorbide-5-Nitrae-oxaspiro ＜ 4.4 ＞ nonane；4- pentenyl 5- oxygen-benzyl -2- deoxidation -4- methoxy Carbonyl-d- furan pentose glycosides；Methyl 5- oxygen-benzyl -3- oxygen-(tert-butyldimethyl silyl) -2- deoxidation -4- methoxycarbonyl group-d- furan Mutter pentoside；1- (2- benzyloxymethyl -3- hydroxyl -2- methoxycarbonyl group -5- oxolane) thymus pyrimidine；4- nitrogen-acetyl group -1- (2- benzyloxymethyl -3- hydroxyl -2- methoxycarbonyl group -5- oxolane) cytosine；4- nitrogen-acetyl group -5- oxygen-benzyl -2- deoxidation - 4- methoxycarbonyl group-cytosine；Methyl -3,3- dimethyl -8- [5- methyl -2 (1- hydrogen), 4- (3 hydrogen)-dioxo pyridine -1- base] - 2,4- dioxa bicyclo- [4.3.0] nonane -6- formic acid esters；Methyl isophthalic acid-(4- methoxybenzyl) -2- benzyloxymethyl -3- hydroxyl -3- Methyl -4- methylene -5- pyrrolidine -2- formaldehyde；Methyl 2- (hydroxyl methoxyl methyl) 1- methoxyl group -5- carbonyl nafoxidine -2- Formic acid esters；(2- cyclopenta-[1,3] dioxolanes -2-) -1- ethyl -2- oxa- -2,3- dihydro -1 hydrogen-indole -3-carboxylic acid second Ester；Benzyloxycarbonyl group-thioprolyl-Thioproline diethyl acetal；Benzyloxycarbonyl group-thioprolyl-Thioproline Two butyral；Benzyloxycarbonyl group-thioprolyl-Thioproline dimethylacetal；Methyl -2 (benzyloxymethyl) -3- hydroxyl - 4- methylene -5- carbonyl nafoxidine -2- formic acid esters；The 1- tert-butyl group -2- methyl -2- (benzyloxymethyl) -5- oXo-tetrahydro pyrrole Cough up -1,2- dicarboxylic acid esters；Methyl -2- benzyloxymethyl -3- t-butyldimethylsilyloxy -4- methyl -5- carbonyl nafoxidine -2- first Acid esters；The 1- tert-butyl group -2- methyl -2 (benzyloxymethyl) -3- hydroxyl -4- methylene -5- oxo-pyrrolidine -1,2- dicarboxylic acid esters； The 5- tert-butyl group -6- methyl -6- (benzyloxymethyl) -2- methyl -4- oxo hexahydro -5 hydrogen-pyrroles [3,4-d] oxazole -5,6- dioctyl phthalate Ester；Methyl isophthalic acid-(3,4- dihydro -1 hydrogen-different phendioxin-yl) cyclopentane-carboxylic acid ester；The tert-butyl group -1- (1- ethyoxyl -3- phenyl alkene Propyl group) -2- carbonyl cyclopentane-carboxylic acid ester；The 1- tert-butyl group -2- methyl -2 (benzyloxymethyl) pyridine -1,2- dicarboxylic acid esters；Nitrogen-(uncle Butoxy carbonyl)-α-(methoxyl methyl) ethyl prolinate；Nitrogen-(tertbutyloxycarbonyl)-α-(tertbutyl methyl) ethyl prolinate；1- The tert-butyl group -2- methyl 2- (benzyloxymethyl) nafoxidine -1,2- dicarboxylic acid esters；3- benzyloxymethyl -1- (2,6- dimethyl benzene) -5- OXo-tetrahydro pyrroles's -3- methyl formate；Ethyl 1- benzyl -2- (diethoxy methyl) nafoxidine -2- formic acid esters；2- benzyloxy first Base -1- methyl-tetrahydro pyrroles's -2- methyl formate；9- methoxyl methyl-fluorenes formic acid-(9)-methyl ester；9- ethoxymethyl-fluorenes formic acid- (9)-methyl ester；9- methoxyl methyl-fluorenes formic acid-(9)-ethyl ester；9- methoxyl methyl-fluorenes formic acid-(9)-N-butyl；9- methoxyl methyl- Fluorenes formic acid-(9)-isobutyl ester；9- methoxyl methyl-fluorenes formic acid-(9)-isopropyl ester；9- ethoxymethyl-fluorenes formic acid-(9)-ethyl ester；9- Ethoxymethyl-fluorenes formic acid-(9)-N-butyl；9- ethoxymethyl-fluorenes formic acid-(9)-isobutyl ester；9- ethoxymethyl-fluorenes formic acid- (9)-isopropyl ester；Two ＜ 9- methoxycarbonyl groups-fluorenes -9- base ＞-ether；3- ＜ 1- ＜ 2- (indol-3-yl) -1- oxo-ethyl ＞ ＞ -2- first Epoxide -3- azabicyclic ＜ 3.2.1 ＞ eight -6 alkene -7- ethyl -1- methyl formate；Methyl -2- methoxy dibenzo bicyclic-＜ 3.2.1 ＞ Octadiene -1- formic acid esters；Methyl-benzyloxymethyl -2- methyl-ring amyl- 2- alkene -1- formic acid esters；Methyl -4- [(tertbutyloxycarbonyl) Amino] -1- ethoxymethyl-ring amyl- 2- alkene -1- formic acid esters；8- benzyloxy -1- carbethoxyl group -5,7,7- trimethyl -2- (propane - 2- methene base) bicyclo- [3.3.0] oct-2-ene；Methyl 1,1- bis- (methylol) -3- methoxyl group -1,2,3,3a, 6,6a- hexahydros penta Alkene -3a- formic acid esters；Methyl 1- (tertiary butyl dimethyl Si methyl) -1- two (methylol) -3- methoxyl group -1,2,3,3a, 6, 6a- hexahydro amylene -3a- formic acid esters；Methyl 1,1- bis- (benzyloxymethyl) -3- methoxyl group -1,2,3,3a, 6,6a- hexahydro amylenes - 3a- formic acid esters；1,2,3,4,5- five poly- (methoxycarbonyl group) -5- (methoxyl methyl) cyclopentadiene；
Six-membered cyclic ether ester compound:
Benzyloxymethyl-methyl cyclohexanecarboxylaand；Ethyl 8- benzyloxymethyl-Isosorbide-5-Nitrae-dioxo-spiral shell [4,5] decane -8- formic acid Ester；2- benzyloxymethyl -2- carbethoxyl group Hexalin；2- benzyloxymethyl -2- carbethoxyl group -1- (oxolane -2- base) oxygen hexamethylene Alkane；4- (DOX -2- base)-(1,1 '-dicyclohexyl) -4- methyl formate；Ethyl -1- (benzyloxymethyl) -4,4- bis- Fluorine naphthenic acid ester；6- methoxyl methyl-Isosorbide-5-Nitrae-dioxa-spiral shell [4.5] decane -6- Ethyl formate；2- methoxyl methyl -2- ethoxy Carbonyl -6- methyl cyclohexanol；1- diethoxy methyl-cyclohexyl base Ethyl formate；Methoxychlor methyl-cyclohexyl base methyl formate；Spiral shell ＜ bis- Ring ＜ 3.3.1 ＞ nonane -2,2 '-＜ 1.3 ＞ dioxa -2,2 '-[1.3] dioxolanes ＞ 1- butyric acid-methyl ester；1- benzyloxymethyl -4- two Methoxycyclohexyl-Ethyl formate；Benzyloxymethyl -4- methoxycyclohexyl-Ethyl formate；Ethyl -4- methyl isophthalic acid-methoxy first Base -4- trimethylsiloxy group hexahydrobenzoid acid ester；1- methoxyl methyl-methyl cyclohexanecarboxylaand；Methyl 1- (3,4- dihydro -1 hydrogen - Different phendioxin-yl) cyclopenta formic acid esters；Tertiary butyl-4-hydroxy -1- (methoxyl methyl) naphthenic acid ester；The tert-butyl group -4- (uncle Butyldimethyl silica) -1- (methoxyl methyl) naphthenic acid ester；The tert-butyl group -4- (5- aminopyridine -2- epoxide) -1- (methoxy Methyl) naphthenic acid ester；The tert-butyl group -1- methoxyl methyl 4- (5- nitropyridine 2- epoxide) naphthenic acid ester；1- (2- methoxy Base-ethoxymethyl)-cyclohexyl ethyl formate；Ethyl -4,4- bis- fluoro- 1- (methoxyl methyl) hexahydrobenzoid acid ester；4- benzyloxy first Base-piperidines-Isosorbide-5-Nitrae-dioctyl phthalate 1- tertiary butyl ester -4- ethyl ester；4- benzyloxymethyl-piperidine-4-ethyl formate；Ethyl 1- ((benzyloxy Methyl) methyl) 2- oxocyclohex alkane formic acid esters；2- benzyloxymethyl -2- carbethoxyl group Hexalin；2- benzyloxymethyl -2- ethoxy carbonyl Base -1- (Pentamethylene oxide. -2- base)-oxygen-hexamethylene；4- methoxyl methyl piperidine-4-ethyl formate；5- methoxyethyl -2- phenyl - [1.3] dioxane -5- methyl formate；2- oxa- six rings-oxygen-furan-[1.3] dithia six ring -2- Ethyl formate；Diethyl Base -3- phenyl -6,6- (ethylene dioxy) -2 oxo -3- azabicyclic ＜ 3.3.1 ＞ nonane -1,5- dicarboxylic acid esters；Methyl tetrahydrochysene- (3,4- dihydro -1 hydrogen-different phendioxin-yl) -2 hydrogen-pyrans -4- formic acid esters；Methyl tetrahydrochysene-(3,4- dihydro -1 hydrogen-different phendioxin - Base) -2 hydrogen-pyrans -4- formic acid esters；Methyl 1- (3,4- dihydro -1 hydrogen-different phendioxin-yl) naphthenic acid ester；Methyl tetrahydrochysene- 3,4- dihydro -5- methyl isophthalic acid hydrogen-different phendioxin-yl) -2 hydrogen-pyrans -4 formic acid esters；Ethyl 4,4- bis- fluoro- 1- (methoxyl methyl) ring Hexane formic acid esters；Ethyl 2- (methoxyl methyl) tetrahydrochysene -2 hydrogen-pyrans -2- formic acid esters；3- methoxyl methyl -3- carbethoxyl group -1- first Base-cyclohexene (1)；Methyl 2,3,3a, 4,5,7a- hexahydro -3,3a- dimethyl -1,5- bis--＜ 2- trimethyl silicane ethoxy-oxygen ＞ indenes - 7a- formic acid esters；1- benzyloxymethyl -1- methoxycarbonyl group -2,5- cyclohexene；
Heptatomic ring ether acid ester compounds:
Methyl 4- benzyl -7- methoxyl group -3- oxo -3,4- dihydro -2 hydrogen -1,5- benzo thia -4- formic acid esters；4- benzyloxy Methyl -3- (4- methoxybenzyl) -5- methyl -7- oxo -6- oxa- -3- aza-bicyclo [3.2.0] heptane -4- methyl formate；
It is preferably, 9- methoxyl methyl-fluorenes formic acid-(9)-methyl ester；9- ethoxymethyl-fluorenes formic acid-(9)-methyl ester；9- methoxy first Base-fluorenes formic acid-(9)-ethyl ester；9- methoxyl methyl-fluorenes formic acid-(9)-N-butyl；9- methoxyl methyl-fluorenes formic acid-(9)-isobutyl ester； 9- methoxyl methyl-fluorenes formic acid-(9)-isopropyl ester；9- ethoxymethyl-fluorenes formic acid-(9)-ethyl ester；9- ethoxymethyl-fluorenes formic acid- (9)-N-butyl；9- ethoxymethyl-fluorenes formic acid-(9)-isobutyl ester；9- ethoxymethyl-fluorenes formic acid-(9)-isopropyl ester.
The compound of formula () preferably includes the compound of formula ():
Wherein, a, b, c, d and e are carbon atom or the hetero atom in n, o and s；W, x, y and z are 0,1 or 2, r1— r8Definition in group such as formula (), r5-r8For identical or different groups.
The compound of formula () preferably includes the compound of formula ():
Wherein r1-r8Definition in group such as formula (), r5-r8For identical or different groups.
In 5-membered ring compounds shown in formula () or (), particular compound example conveniently has:
Ethyl 1- (1,1- ethylene dioxy ethyl) Pentamethylene. -1- formic acid esters；Ethyl 2- (1- methoxy cyclopentane) -2- methoxy Yl acetate；Methyl 1- (methoxyl methyl) cyclopentane-carboxylic acid ester；1- (benzyloxymethyl) methyl cyclohexanecarboxylaand；1- (4,4,6- tri- Methyl-[1,3] azepine pyrans -2- base)-cyclopenta Ethyl formate；2- chloro- methoxyethyl -1- cyclopenta methyl formate；Two ＜ rings Hexyl methyl formate ＞ dimethyl cellosolve；2- benzyloxy-(1,1- ethylene dioxy ethyl)-cyclopenta Ethyl formate；And methyl isophthalic acid-first Epoxide bicyclo- ＜ 2.2.2 ＞ octyl- 8- alkene -2,6- dicarboxylic acid methyl ester；1- methoxyl group earrings ＜ 2.2.2 ＞ octyl- 9- alkane, trimethyl -1- first Epoxide earrings ＜ 2.2.1 ＞ heptane -2,6,10- front three acid esters；1- methoxyl group -1- cyclopentanecarboxyalte base -3 phenyl-acryloyl；2- Benzyloxymethyl -2- carbethoxyl group -1- (Pentamethylene oxide. -2- oxygen) oxygen Pentamethylene.；2- benzyloxy -2- carbethoxyl group-cyclopentanol；First Base 1- (1- methoxyethyl) cyclopentanecarboxylic acid ester；2- methyl -2 (1- cyclopenta Ethyl formate -1- base) -4- methylene -1,3- oxo Propane；Methyl-(3,4- dihydro -1 hydrogen-different pyrans -1- base) cyclopenta formic acid esters；Ethyl 1- (methoxyl methyl) cyclopentane-carboxylic acid Ester；Methyl isophthalic acid-(ethoxymethyl) cyclopentane-carboxylic acid ester；2- benzyloxymethyl -1- Ketocyclopentane-Ethyl formate；1- benzyloxymethyl-four Hydrogen pyrroles's -2- methyl formate；Methyl-hexahydro -2,2,7- trimethyl -6- oxo [1,3] dioxy [5,4-b] pyrroles -4a- formic acid Ester；Methyl -2- benzyloxymethyl -5- carbonyl nafoxidine -2- formic acid esters；Methyl 1- (4- chlorobenzene) -3- (methoxyl methyl) -4,5- Dicarbapentaborane pyrroles's -3- formic acid esters；3- methoxyl methyl-nafoxidine -3- methyl formate；1- tert-Butoxycarbonylmethyl -3- methoxy first Base-nafoxidine -3- formic acid esters；1- benzyl -3- methoxyl methyl-nafoxidine -3- methyl formate；2- ethoxymethyl-tetrahydrochysene pyrrole Cough up -1,2- dioctyl phthalate 1- tert-butyl ester 2- methyl ester；2- isopropoxymethyl-nafoxidine -1,2- dioctyl phthalate 1- tert-butyl ester 2- ethyl ester；First Base 3- methoxyl methyl -1- (3- tolyl) -4,5- dicarbapentaborane nafoxidine -3- formic acid esters；Methyl 3- methoxyl methyl -1- (4- fluorine Phenyl) -4,5- dicarbapentaborane nafoxidine -3- formic acid esters；Methyl 3- methoxyl methyl -1- (4- bromophenyl) -4,5- dicarbapentaborane tetrahydrochysene Pyrroles's -3- formic acid esters；Methyl 1- (4- hydroxy phenyl) -3- methoxyl methyl -4,5- dicarbapentaborane nafoxidine -3- formic acid esters；Ethyl 3- ethoxymethyl -1- phenyl -4,5- dicarbapentaborane nafoxidine -3- carboxylate；Ethyl 3- ethoxymethyl -1- (3 tolyl) -4,5- Dicarbapentaborane nafoxidine -3- carboxylate；3- methoxyl methyl -2- carbonyl-oxolane -3- Ethyl formate；3- isopropoxymethyl -2- Carbonyl-oxolane -3- Ethyl formate；1- (4,4,6- trimethyls-[1,3] oxazines -2- base)-cyclopenta Ethyl formate；Methyl- 3- ethyl -2- ＜ (2- trimethyl silicane ethyoxyl) methoxyl methyl ＞-Isosorbide-5-Nitrae-dioxo spiro ＜ 4.4 ＞ nonane -2- formic acid esters；Methyl 5- Oxygen-phenyl -2- deoxidation -4- methoxycarbonyl group-d- furan pentose glycosides；2- benzyloxymethyl -3- (2- methoxyvinyl) -2- methoxy carbonyl Base-Isosorbide-5-Nitrae-oxaspiro ＜ 4.4 ＞ nonane；4- pentenyl 5- oxygen-benzyl -2- deoxidation -4- methoxycarbonyl group-d- furan pentose glycosides；Methyl 5- oxygen-benzyl -3- oxygen-(tert-butyldimethyl silyl) -2- deoxidation -4- methoxycarbonyl group-d- furan pentose glycosides；1- (2- benzyloxymethyl- 3- hydroxyl -2- methoxycarbonyl group -5- oxolane) thymus pyrimidine；4- nitrogen-acetyl group -1- (2- benzyloxymethyl -3- hydroxyl -2- methoxy Carbonyl -5- oxolane) cytosine；4- nitrogen-acetyl group -5- oxygen-benzyl -2- deoxidation -4- methoxycarbonyl group-cytosine；Methyl -3, 3- dimethyl -8- [5- methyl -2 (1- hydrogen), 4- (3 hydrogen)-dioxo pyridine -1- base] -2,4- dioxa bicyclo- [4.3.0] nonyl Alkane -6- formic acid esters；Methyl isophthalic acid-(4- methoxybenzyl) -2- benzyloxymethyl -3- hydroxy-3-methyl -4- methylene -5- pyrrolidine - 2- formaldehyde；Methyl 2- (hydroxyl methoxyl methyl) 1- methoxyl group -5- carbonyl nafoxidine -2- formic acid esters；(2- cyclopenta-[1,3] two Butyl oxide link -2-) -1- ethyl -2- oxa- -2,3- dihydro -1 hydrogen-indole -3-carboxylic acid ethyl ester；Benzyloxycarbonyl group-thioprolyl- Thioproline diethyl acetal；Benzyloxycarbonyl group-thioprolyl-Thioproline two butyral；Benzyloxycarbonyl group-thio dried meat ammonia Acyl group-Thioproline dimethylacetal；Methyl -2 (benzyloxymethyl) -3- hydroxyl -4- methylene -5- carbonyl nafoxidine -2- Formic acid esters；The 1- tert-butyl group -2- methyl -2- (benzyloxymethyl) -5- oXo-tetrahydro pyrroles -1,2- dicarboxylic acid esters；Methyl -2- benzyloxy Methyl -3- t-butyldimethylsilyloxy -4- methyl -5- carbonyl nafoxidine -2- formic acid esters；The 1- tert-butyl group -2- methyl -2 (benzyloxy Methyl) -3- hydroxyl -4- methylene -5- oxo-pyrrolidine -1,2- dicarboxylic acid esters；The 5- tert-butyl group -6- methyl -6- (benzyloxy first Base) -2- methyl -4- oxo hexahydro -5 hydrogen-pyrroles [3,4-d] oxazole -5,6- dicarboxylic acid esters；Methyl isophthalic acid-(3,4- dihydro -1 hydrogen - Different phendioxin-yl) cyclopentane-carboxylic acid ester；The tert-butyl group -1- (1- ethyoxyl -3- phenyl allyl) -2- carbonyl cyclopentane-carboxylic acid ester； The 1- tert-butyl group -2- methyl -2 (benzyloxymethyl) pyridine -1,2- dicarboxylic acid esters；Nitrogen-(tertbutyloxycarbonyl)-α-(methoxyl methyl) dried meat ammonia Acetoacetic ester；Nitrogen-(tertbutyloxycarbonyl)-α-(tertbutyl methyl) ethyl prolinate；The 1- tert-butyl group -2- methyl 2- (benzyloxymethyl) four Hydrogen pyrroles -1,2- dicarboxylic acid esters；3- benzyloxymethyl -1- (2,6- dimethyl benzene) -5- oXo-tetrahydro pyrroles's -3- methyl formate；Second Base 1- benzyl -2- (diethoxy methyl) nafoxidine -2- formic acid esters；2- benzyloxymethyl -1- methyl-tetrahydro pyrroles's -2- formic acid first Ester.
The compound of formula () further preferably includes the compound of formula ():
Wherein r1-r8Definition in group such as formula ().
Its preferred compound is the compound of formula ():
Wherein r1-r4Definition in group such as formula (), r ' is hydrogen that is identical or differing, halogen atom, straight or branched C1-c20Alkyl, c3-c20Cycloalkyl, c6-c20Aryl, c7-c20Alkaryl and c7-c20Aralkyl.
In 5-membered ring compounds shown in formula () or (), particular compound example conveniently has:
9- methoxyl methyl-fluorenes formic acid-(9)-methyl ester；9- ethoxymethyl-fluorenes formic acid-(9)-methyl ester；9- methoxyl methyl-fluorenes first Acid-(9)-ethyl ester；9- methoxyl methyl-fluorenes formic acid-(9)-N-butyl；9- methoxyl methyl-fluorenes formic acid-(9)-isobutyl ester；9- methoxy Methyl-fluorenes formic acid-(9)-isopropyl ester；9- methoxyl methyl-fluorenes formic acid-(9)-benzyl ester；9- ethoxymethyl-fluorenes formic acid-(9)-ethyl ester； 9- ethoxymethyl-fluorenes formic acid-(9)-benzyl ester；9- ethoxymethyl-fluorenes formic acid-(9)-N-butyl；9- ethoxymethyl-fluorenes formic acid- (9)-isobutyl ester；9- ethoxymethyl-fluorenes formic acid-(9)-isopropyl ester；9- methoxybenzyl-fluorenes formic acid (9)-benzyl ester；Two ＜ 9- methoxy carbonyls Base-fluorenes -9- base ＞-ether；1,2,3,4,5- five poly- (methoxycarbonyl group) -5- (methoxyl methyl) cyclopentadiene.
It is preferably, 9- methoxyl methyl-fluorenes formic acid-(9)-methyl ester；9- ethoxymethyl-fluorenes formic acid-(9)-methyl ester；9- methoxy first Base-fluorenes formic acid-(9)-ethyl ester；9- methoxyl methyl-fluorenes formic acid-(9)-N-butyl；9- methoxyl methyl-fluorenes formic acid-(9)-isobutyl ester； 9- methoxyl methyl-fluorenes formic acid-(9)-isopropyl ester；9- ethoxymethyl-fluorenes formic acid-(9)-ethyl ester；9- ethoxymethyl-fluorenes formic acid- (9)-N-butyl；9- ethoxymethyl-fluorenes formic acid-(9)-isobutyl ester；9- ethoxymethyl-fluorenes formic acid-(9)-isopropyl ester.
The ring of the present invention is replaced ether acid ester and can be synthesized by various.One of them is to be closed by following formula three-step reaction Become: by corresponding ring substituted compound be prepared into cyclic hydrocarbon radical replace formic acid, then with corresponding alcohol r1Oh reaction esterification is formic acid esters, Or replace formic acid esters with suitable esters precursor direct addition for cyclic hydrocarbon；By upper step product and the precursor suitably containing oxyl Addition obtains final product product.
Particularly as follows: step a is to react corresponding ring substituted compound and carbon dioxide and alkyl lithium reagents, or and alkyl Dimethyl ester and sodium hydride reaction are prepared into cyclic hydrocarbon radical and replace formic acid (can be found in us4564700a1)；
Step b is by upper step product and corresponding alcohol r1Oh reaction esterification be formic acid esters, or with suitable esters precursor Direct addition for cyclic hydrocarbon replace formic acid fat (can be found in journal of the chemical society, 1949, p2182, 2185)；
Step c is that (upper step product be can be found in analytical with to prepare with the precursor addition suitably containing oxyl chemistry,vol.32,no.4,april1960).
Step a of above-mentioned preparation method and step c order can exchange, you can go up formic acid (ester) base again first to go up ether.
The ingredient of solid catalyst for olefinic polymerization of the present invention, comprises titanium compound, magnesium compound and is selected from described The ring of formula ()-() replaces the product of ether acid ester compounds, and the precursor of described magnesium compound is selected from least one: Rmgx, mgr2, mgcl2Mroh, mg (or)2, xnmg(or)2-n, mgcl2/sio2, or the mixture of magnesium halide and alcohol titanium, in formula M is the number of 0.1-6, and 0 < n < 2, x is halogen, and r is c1-c20Alkyl；The formula of described titanium compound is tixn(or)4-n, in formula R is the alkyl of 1-20 for carbon number, and x is halogen, n=1-4.
The magnesium compound of the present invention preferably employs magnesium hydrocarbyloxy compound.
Another alcohol adduct preferably employing magnesium dihalide of the magnesium compound of the present invention.
The magnesium compound of the present invention further preferably employs liquid magnesium compound.
The titanium compound of the present invention includes titanium tetrachloride, titanium tetrabromide, titanium tetra iodide or alkoxy titanium, alkyl halide Titanium such as methoxytitanium trichloride, ethyoxyl titanous chloride., propoxyl group titanous chloride., nbutoxytitanium trichloride, dimethoxy two Titanium chloride, diethoxy titanium chloride, dipropoxy titanium chloride, two n-butoxy titanium chloride, trimethoxy titanium chloride, three Ethyoxyl titanium chloride, tripropoxy titanium chloride or three n-Butoxyl titanium-chlorides.Can apply one or more in these halogenated titaniums It is used in mixed way.Wherein preferably employ titanium tetrachloride.
The preparation of the ingredient of solid catalyst of the present invention can be carried out according to several method.
According to one of which method, use ticl4Or aromatic hydrocarbons (the such as toluene, dimethylbenzene etc.) solution of titanium alkoxides is permissible React in -25-0 DEG C of two magnesium hydrocarbyloxy compound with such as dialkoxy magnesium or two aryloxy group magnesium etc, and at 80-130 DEG C Carry out halogenation.Use ticl4The process that carries out of arene solution can be repeated one or more times, and repeatedly such process in plus The ring entering formula ()-() replaces ether acid ester compounds.For example can refer to the solids containing titanium catalysis disclosed in us5077357 The preparation method of agent component is prepared: sequentially adds magnesium ethylate, purity titanium tetraethoxide, orthoresol, ethanol and chlorobenzene, stirring； By ticl4/ chlorobenzene solution rapidly joins in aforesaid liquid, heats up until completely dissolved, is continuously heating to specified temp；Using n2 Bubbling continues stirring certain time after taking away ethanol synthesis thing, then be washed once using hot chlorobenzene, and isobutyltrimethylmethane. washes twice, then n2Dry up and can obtain carrier.Or according to another example: successively by ticl4, purity titanium tetraethoxide, magnesium ethylate and orthoresol add chlorine In benzene, stirring；Add ethanol, after magnesium ethylate dissolving, under high temperature, continue stirring 3h；Then filtered while hot is washed using warm chlorobenzene Wash once, isobutyltrimethylmethane. washed once, last n2It is dried.
According to another kind of method, the alcoholates of magnesium or chlorohydrin and the ring containing formula () () in the solution Replace the ticl of the excess of ether acid ester compounds4React at a temperature of 80-135 DEG C.According to preferred method, formula can be tixn(or)4-nTitanium compound, the alkyl that in formula, r is 1 20 for carbon number, x be halogen, n=1-4；Preferably ticl4, with It is mgcl from formula2Mroh adduct reaction and prepare ingredient of solid catalyst, in formula m be 0.1-6 number, preferably 2 to 3.5, and r is the alkyl with 1-20 carbon atom.Adduct can be conveniently made spherical by the following method: not with plus In the presence of the miscible unreactive hydrocarbons of compound, alcohol and magnesium chloride mixing make the rapid chilling of this emulsion, so that adduct is with spherical The form solidification of grain.Spherical mgcl according to the preparation of this process2Mroh adduct example description be found in us4399054 and In us4469648.So obtained adduct can directly be reacted with titanium compound, or it can first pass through thermal control in advance Dealcoholization (80-130 DEG C) is generally below 3, preferably between 0.1 and 2.5 to obtain a kind of adduct, the molal quantity of wherein alcohol. Can be by adduct (dealcoholysis or itself) be suspended in cold ticl4To carry out in (general -25-0 DEG C) closing with titanizing The reaction of thing；Heat the mixture to 80-130 DEG C and keep 0.5-2 hour at this temperature.Use ticl4The process carrying out can To carry out once or repeatedly.With ticl4The ring that formula () () can be added during process replaces ether acid ester compounds Processed, this process can be repeated once or repeatedly.
Another kind of method preparing ingredient of solid catalyst of the present invention is included, by anhydrous magnesium chloride and formula () () Ring replace ether acid ester compounds grind together under conditions of magnesium dichloride activates.So obtained product can be With excessive ticl at a temperature of 80-130 DEG C4Process one or many.Washed with hydro carbons volume after process until not chloride from Son.According to further method, will be taken by the ring of magnesium dichloride, titanium compound and formula () () to anhydrous state For ether acid ester compounds be co-mulled and made into obtained from product, using such as 1,2- dichloroethanes, chlorobenzene, dichloromethane etc Halogenated hydrocarbons are processed.This process carries out 1-4 hour at a temperature of between 40 DEG C to halogenated hydrocarbons boiling point.Then generally with oneself The inertia hydro carbons volume of alkane etc obtains product to wash.
According to another kind of method, magnesium dichloride is carried out according to known methods pre-activate, then at about 80-135 DEG C At a temperature of with excessive ticl4Process, the ring wherein containing formula () () in the solution replaces ether acid ester compounds.With ticl4Process repeatedly and solid is carried out to remove any ticl for reaction with hexane4.
Further method includes, and may further reference the preparation of the solids containing titanium catalytic component disclosed in cn1208045 Method is prepared: first makes liquid in the presence of a kind of compound selected from alcohol, phenol, ketone, aldehyde, ether, amine, pyridine and ester at low temperature Body magnesium compound contacts with liquid titanium compound, is settled out solid, generally -70-200 DEG C of temperature during contact, preferably - 30-130 DEG C, use the ring of formula ()-() to replace ether acid ester compounds in contact process and process.
Another kind of method of the ingredient of solid catalyst of the present invention includes: magnesium compound is dissolved in by organic epoxy compound In the dicyandiamide solution of thing, organic phosphorus compound and inert diluent composition, mix with titanium compound after forming homogeneous solution, helping In the presence of precipitation agent, wash out solidss；The ring of this solids formula ()-() replace ether acid ester compounds process so as to It is carried on solidss, if necessary, then processed and obtained with titanium tetrahalide and inert diluent, wherein precipitation additive is organic acid One of acid anhydride, organic acid, ether, ketone.In terms of every mole of magnesium halide, organic epoxy compound thing rubs described each component for 0.2-10 You, organic phosphorus compound is 0.1-3 mole, and precipitation additive is 0.03-1.0 mole, the halogenide of transition metal ti and its derivative Thing is 0.5-150 mole.
The ingredient of solid catalyst of the present invention, can also be using in sio2, inorganic oxide or the porous resin such as aluminium oxide The magnesium compound of upper load as carrier prepare, then by known to method activated, then in about 80-135 DEG C of temperature The lower ticl with excess4Process, add the ring having formula ()-() to replace ether acid ester compounds in processing procedure.
(general crystal magnesium halide compound with regular structure, can load the magnesium halide that above-mentioned reaction results in activity morphology Ti seldom, thus catalysis activity is low, will prepare highly active supported catalyst, and magnesium halide has to pass through activation processing.Activation Processing method includes being made into crystallite, so that active center is carried on halogenation magnesium surface, side with method physically and/or chemically Edge and fault location, what this was processed be suitable for loads the magnesium halide crystallite of ti and is " magnesium halide in active ").In addition to these reactions, Also being known to other methods in document makes to be formed the halogenation in activity morphology by the compound initial substance different from magnesium halide Magnesium.
In any preparation method, the ring of formula ()-() is replaced ether acid ester compounds and directly can be added with itself Enter or carried out by optional mode, such as by being obtained in situ using suitable precursor, this suitably front physical ability is resonable think to The known chemical reaction of such as esterification, ester exchange etc. is for example relied on to complete to change in electron compound.Generally, with respect to mgcl2For, with 0.01-5, the preferably mol ratio of 0.05-2.0 to be replaced ether acid esterification using the ring of formula ()-() and is closed Thing.
The ingredient of solid catalyst of the present invention by by the reaction of known method and organo-aluminum compound change into for The catalyst of olefinic polymerization.Especially, it is an object of the present invention to provide a kind of be used for alkene ch2What=chr was polymerized urges Agent, wherein r are hydrogen or the hydrocarbyl group containing 1-12 carbon atom, and this catalyst includes the product of following substance reaction:
A () is of the present invention to replace ether acid esterification conjunction containing mg, ti and halogen and the ring selected from formula ()-() The ingredient of solid catalyst of thing；
B () at least one formula is alrnx(3-n)Organo-aluminum compound, in formula r be hydrogen, the alkyl of carbon number 1-20； X is halogen, and n is the integer of 0≤n≤3；With, optionally,
(c) at least one external donor compound.
Preferably, organo-aluminum compound (b) is selected from such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three normal-butyls The trialkyl compound of aluminum, tri-n-hexyl aluminum, trioctylaluminum etc.It is also possible to using trialkylaluminium and aluminum alkyl halide, Alkyl aluminum hydride or such as alet2Cl and al2et3cl3Etc alkylaluminium sesquichloride mixture, can also use Alkyl chloride oxygen alkane.
For the application needing good isotacticity, external donor compound can be used.External donor compound selects Self-drifting is rnsi(or1)4-nSilicone compounds, r and r in formula1For c1-c18Alkyl, optionally also hetero atom；N be 0≤ The integer of n≤3.
Described silicone compounds are concretely: trimethylmethoxysilane, trimethylethoxysilane, three n-pro-pyl first TMOS, three n-pro-pyl Ethoxysilanes, three normal-butyl methoxy silane, triisobutyl Ethoxysilane, thricyclohexyl first Base silane, thricyclohexyl Ethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, diη-propyl diformazan TMOS, diisopropyl dimethoxy silane, diη-propyl diethoxy silane, diisopropyldiethoxysilane, two just Butyl diethoxy silane, diisobutyl diethoxy silane, di-t-butyl dimethoxysilane, di-t-butyl dimethoxy silicon Alkane, di-n-butyl dimethoxysilane, second, isobutyl dimethoxy silane, di-t-butyl diethoxy silane, di-n-butyl two Ethoxysilane, n-butylmethyldimethoxyforane, two (2- ethylhexyl) dimethoxysilane, two (2- ethylhexyls) two Ethoxysilane, Dicyclohexyldimethoxysilane, dicyclohexyl diethoxy silane, dicyclopentyl dimethoxyl silane, two Cyclopenta diethoxy silane, Cyclohexyl Methyl Dimethoxysilane, cyclohexyl methyl diethoxy silane, cyclohexyl-ethyl two Methoxy silane, cyclohexyl isopropyl dimethoxysilane, cyclohexyl-ethyl diethoxy silane, cyclopentyl-methyl dimethoxy Silane, cyclopentyl ethyl diethoxy silane, cyclopenta isopropyl diethoxy silane, cyclopenta isobutyl group dimethoxy silicon Alkane, cyclohexyl n-pro-pyl dimethoxysilane, cyclohexyl n-pro-pyl diethoxy silane, cyclohexyl normal-butyl diethoxy silicon Alkane, phenyl-methyl dimethoxysilane, phenyl-methyl diethoxy silane, amyl group ethyldimethoxysilane, amyl group ethyl two Ethoxysilane, cyclohexyldimethyl methoxy silane, cyclohexyl diethylmethoxysilane, cyclohexyl diethyl ylmethoxy silicon Alkane, cyclohexyl diethylethoxysilane, 2- ethylhexyl trimethoxy silane, cyclohexyl dimethoxysilane, cyclohexyl two Ethoxysilane, 2- ethylhexyl triethoxysilane, ethyl trimethoxy silane, ethyl triethoxysilane, n-pro-pyl three Methoxy silane, n-pro-pyl triethoxysilane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, normal-butyl three Methoxy silane, trimethoxysilane, tert-butyl trimethoxy silane, ne-butyltriethoxysilaneand, cyclohexyl three Methoxy silane, cyclohexyltriethyloxysilane, cyclopentyl-trimethoxy-silane, cyclopenta triethoxysilane, vinyl three Methoxy silane, VTES, 2- ethylhexyl trimethoxy silane, 2- ethylhexyl triethoxysilane, Amyltrimethoxysilane, amyl triethoxysilane, tetramethoxy-silicane, tetraethoxysilane, cyclohexyl ring amyl group diformazan TMOS, cyclohexyl ring amyl group diethoxy silane, cyclohexyl ring amyl group dipropoxy silane, 3- methyl cyclohexane cyclopentyl Dimethoxysilane, 4- methyl cyclohexane cyclopentyl dimethoxysilane, 3,5- dimethyleyelohexane cyclopentyl dimethoxy silicon Alkane, 3- methyl cyclohexane butylcyclohexyl dimethoxysilane, two (3- methylcyclohexyl) dimethoxysilane, 4- methyl cyclohexane basic ring Hexyl dimethoxysilane, two (4- methylcyclohexyl) dimethoxysilane, 3,5- dimethyleyelohexane butylcyclohexyl dimethoxy Silane, two (3,5- Dimethylcyclohexyl) dimethoxysilane, tetrapropoxysilane, four butoxy silanes.In these organosilicons First-selected in compound: diη-propyl dimethoxysilane, diisopropyl dimethoxy silane, di-n-butyl dimethoxysilane, Second, isobutyl dimethoxy silane, di-t-butyl dimethoxysilane, di-n-butyl diethoxy silane, tert-butyl group trimethoxy Silane, Dicyclohexyldimethoxysilane, dicyclohexyl diethoxy silane, Cyclohexyl Methyl Dimethoxysilane, cyclohexyl Ethyl diethoxy silane, cyclohexyl-ethyl dimethoxysilane, cyclohexyl-ethyl diethoxy silane, cyclopentyl-methyl diformazan TMOS, cyclopentyl-methyl diethoxy silane, cyclopentyl ethyl dimethoxysilane, cyclohexyl ring dicyclopentyldimetoxy silicon Alkane, cyclohexyl ring amyl group diethoxy silane, 3- methyl cyclohexane cyclopentyl dimethoxysilane, 4- methyl cyclohexane cyclopentyl Dimethoxysilane and 3,5- dimethylcyclopentyl dimethoxysilane etc..These compounds c can be used alone or mixes and makes With.
The example of preferably silicon compound has Cyclohexyl Methyl Dimethoxysilane；Diisopropyl dimethoxy silane；Two Normal-butyl dimethoxysilane；Second, isobutyl dimethoxy silane；Dimethoxydiphenylsilane；Phenyl triethoxysilane； Methyl-t-butyldimethoxysilane；Dicyclopentyl dimethoxyl silane；2- ethyl piperidine base -2- t-butyldimethoxysilane (1,1,1- tri- fluoro- 2- propyl group) -2- ethyl piperidine base dimethoxysilane and (1,1,1- tri- fluoro- 2- propyl group)-methyl and first TMOS, cyclohexyl trimethoxy silane；Tert-butyl trimethoxy silane and tertiary hexyl trimethoxy silane.
The catalyst of the present invention can be used for alkene ch2In=chr (co) polymerization, described alkene is ethylene, propylene, 1- fourth Alkene, 4-methyl-1-pentene, 1- hexene and 1- octene.
In order to apply the catalyst in the present invention to carry out olefinic polymerization, homopolymerization and copolymerization can be applied above by component Catalyst prepared by a, b, c.The titanium that the mol ratio of generally component b and component a is contained in component a for the every mol of 1-1000mol is former The every mol of son, preferably 50-800mol is contained in the titanium atom in component a；Component c is 0.002-10 with the mol ratio of component a, excellent Elect 0.01-2, preferably 0.01-0.5 as.
The charging sequence of each component is arbitrary, is added at first in paradigmatic system with component b, is subsequently adding component c, Component a is added to be preferred afterwards.
Polymerization technique in the present invention can be carried out there being solvent or in the case of not having solvent.Olefinic monomer can be gas Phase or liquid phase.Addition hydrogen can be used as molecular weight regulator further.Certainly polymerization can also not have molecular weight regulator In the case of carry out.Polymerization temperature is not higher than 200 DEG C, preferably 20-100 DEG C, more preferably 40-80 DEG C of temperature.Polymerization pressure is not 10mpa to be exceeded, preferably 1-5mpa.Continuous polymerization or batch polymerization process can be applied.And polyreaction can divide one Step, two steps or multistep are carried out.
Apply catalyst of the present invention to carry out homopolymerization or the alkene of copolymerization includes, linear alkene: ethylene, propylene, 1- fourth Alkene, 1- amylene, 1- hexene, 1- heptene, 1- nonene, 1-decene；Branched-chain alkene is such as: 3-methyl-1-butene and 4- methyl-1-pentene Alkene；Alkadienes are such as: butadiene, vinylcyclopentene and VCH.Catalyst of the present invention is preferably applied to gather In ethylene and polypropylene.These alkene can be independent or multiple be used in mixed way.
The polymerization (herein referring to mass polymerization) of the alkene that application catalytic component a, b, c of the present invention are carried out is it is recommended that carry out Prepolymerization is increasing isotacticity, particle properties of the living polymer of catalyst etc..This prepolymerization technology can be equally used for benzene Ethylene homo.
In prepolymerization technology, the charging sequence of each component and monomer is arbitrary.Preferably first component b is added to and contains Have in inertia or the alkene gas that will be polymerized, after adding component a, then add one or more alkene to be polymerized.? It is proposed that the alkene that component b is added to noble gases or will be polymerized during the alkene of application organosilan is prepolymerized In the pre-polymerization assembly system of gas, it is subsequently adding component c, is subsequently adding component a, finally add alkene.
The present invention using the polyfunctional compound with ad hoc structure, that is, as shown in formula () containing an ehter bond With the ring substituted compound of an acid esters key, because the oxygen of ehter bond and ester bond has stronger coordination effect, and in catalyst Relatively stable in preparation process, the activity therefore to catalyst and isotacticity play active and effective effect.And same Ehter bond and ester bond is contained respectively, the advantage of the comprehensive two kinds of different functional groups of energy, especially to catalyst activity in compound Play certain adjustment effect with the control aspect of polymer architecture.
Specific ring contained by such compound of the present invention replaces structure, have steric effect and can fix ether, The spatial configuration of acid ester functionality, in the formation participating in catalyst active center and to the stereoselectivity tool improving catalyst Play the role of positive.
The present inventor finds in an experiment, prepares Ziegler-Natta catalyst such compound is used for electron donor Group timesharing, can make catalytic component have excellent activity, and obtain the polymeric articles with high isotactic.By the present invention's Compound is separately to several big most generation such as magnesium ethylate system, chlorination magnesium alcoholate system and magnesium chloride solution modeling system In the preparation system of the ziegler natta catalyst of table, the catalyst of gained all has higher compounds content, and this is described Compound has good coordination property and stability；The activity of the catalyst of gained adopts under the conditions of being generally higher than same process The catalyst of conventional fragrant diester electron donor, and there is high stereoselectivity.
Specific embodiment
Further describe the present invention with embodiment below, be conducive to the present invention and its advantage, effect are better understood by, but Described embodiment is merely to illustrate the present invention rather than limits the present invention.
The five-membered ring ether ester compound enumerated in embodiment is only used as example so that the present invention to be described, does not limit the present invention, Other belong to scope but the compound that do not refer in an embodiment, such as hexatomic ring and heptatomic ring ether ester compound also with The compound of embodiment is the same, has similar performance.
Ring replaces the preparation of ether acid ester compounds
The synthesis of embodiment 19- methoxyl methyl-fluorenes formic acid-(9)-methyl ester
Step a: in nitrogen protection under to 1000ml there-necked flask in sequentially add 18g sodium hydride, 50g fluorenes, 150ml first Benzene, opens mechanical agitation, is warming up to 125 DEG C of backflows, keeps reaction 4h；It is cooled to 90 DEG C, toward in flask, be slowly added dropwise 146.1g Diethyl carbonate, drips off in 1.5h, continues reaction 3h after dripping off；It is cooled to 20 DEG C, be slowly dropped into 60g concentrated hydrochloric acid and 75g water Mixture, and control temperature to be less than 40 DEG C；Filter, isolate organic faciess, wash with water to neutrality, organic faciess revolving, obtain Rufous liquid；Revolving gained liquid is flowed back overnight together with the hydrochloric acid of 157.4g acetic acid and 63g10%；Mixture is down to 20 DEG C, point liquid；Add 30%naoh solution after organic faciess revolving, adjust ph value to 8, be extracted with ethyl acetate, retain aqueous phase.Water It is added to concentrated hydrochloric acid regulation ph value to be extracted with ethyl acetate to after 5, retain organic faciess, organic faciess revolving；Product ethyl acetate Dissolving, freezes recrystallization；Filter, crude product is washed with hexane.Obtain clear crystal about 10g, fusing point: 228～230 DEG C.
In step b:250ml there-necked flask, add 9- formic acid fluorenes 2g (9.5mmol), methanol (30ml), concentrated sulphuric acid (0.2ml)； It is heated to reflux 2h；It is cooled to room temperature；Reactant liquor is poured in saturated sodium bicarbonate solution, and ethyl acetate extracts secondary (30ml*2), Merge organic faciess, saturated common salt washes (30ml*1), vacuum distillation obtains yellow solid, oil pump is drained, obtains 1.8g crude product, 62-65 DEG C of fusing point.
Add methanol (20ml), metallic sodium (0.12g, 5mmol) in step c:250ml three neck round bottom flask, treat under ice bath Metallic sodium is completely dissolved after bubble-free emerges, and adds 9- methyl formate fluorenes (0.56g, 2.5mmol), is completely dissolved, in yellow, stirs Chloromethyl methyl ether (0.6g, 7.5mmol) is added after mixing 5min；Stirring 30min, pours in aqueous solution, is extracted with dichloromethane (20ml*2) use ethyl acetate after instead and be extracted twice (50ml*2) merging organic faciess, saturated common salt washes (50ml*1), and revolving is walked Liquid, hexane washs, and obtains product, 126-129 DEG C.
9- methoxyl methyl-fluorenes formic acid-(9)-methyl ester1h-nmr(cdcl3) δ (ppm): 3.370 (s, 3h, ether methyl), 3.660(s, 3h, METH), 3.791 (s, 2h, methylene hydrogen), 7.313-7.345 (t, 2h, aromatic ring hydrogen), 7.408-7.440 (t, 2h, aromatic ring hydrogen), 7.707-7.745 (m, 4h, aromatic ring hydrogen).
The synthesis of embodiment 29- ethoxymethyl-fluorenes formic acid-(9)-N-butyl
With embodiment 1, difference is that the methanol in step b is changed to n-butyl alcohol to synthesis step.1h-nmr(cdcl3)δ (ppm): 0.86 (t, 3h, hydrogen), 1.27 (m, 2h, methylene hydrogen), 1.54 (m, 2h, methylene hydrogen), 3.37 (s, 3h, ether methyl Hydrogen), 3.80 (s, 2h, ether methylene hydrogen), 4.11 (t, 2h, ester group methylene hydrogen), 7.31-7.40 (t, 2h, aromatic ring hydrogen), 7.42-7.43 (t, 2h, aromatic ring hydrogen), 7.72-7.74 (m, 4h, aromatic ring hydrogen).
The synthesis of embodiment 39- methoxyl methyl-fluorenes formic acid-(9)-isobutyl ester
With embodiment 1, difference is that the methanol in step b is changed to isobutanol to synthesis step.1h-nmr(cdcl3)δ (ppm): 0.832-0.0845 (d, 6h, methyl hydrogen), 1.833-1.900 (m, 1h, methine hydrogen), 3.384 (s, 3h, ether methyl Hydrogen), 3.821 (s, 2h, ether methylene hydrogen), 3.887-3.900 (d, 2h, ester group methylene hydrogen), 7.260-7.352 (t, 2h, Aromatic ring hydrogen), 7.408-7.440 (t, 2h, aromatic ring hydrogen), 7.735-7.750 (m, 4h, aromatic ring hydrogen).
The synthesis of embodiment 49- methoxyl methyl-fluorenes formic acid-(9)-isopropyl ester
With embodiment 1, difference is that the methanol in step b is changed to isopropanol to synthesis step.1h-nmr(cdcl3)δ (ppm): 1.179-1.191 (d, 6h, methyl hydrogen), 3.364 (s, 3h, ether methyl hydrogen), 3.768 (s, 2h, ether methylene hydrogen), 5.035-5.085 (m, 1h, methine hydrogen), 7.303-7.335 (t, 2h, aromatic ring hydrogen), 7.392-7.409 (t, 2h, aromatic ring hydrogen), (7.716-7.733 m, 4h, aromatic ring hydrogen).The synthesis of embodiment 59- methoxyl methyl-fluorenes formic acid-(9)-ethyl ester
With embodiment 1, difference is that the methanol in step b is changed to ethanol to synthesis step.1h-nmr(cdcl3)δ (ppm): 1.17-1.20 (t, 3h, methyl hydrogen), 3.37 (s, 3h, ether methyl hydrogen), 3.791 (s, 2h, ether methylene hydrogen), 4.14- 4.19 (m, 2h, ester methylene hydrogen), 7.26-7.42 (t, 2h, aromatic ring hydrogen), 7.42-7.44 (t, 2h, aromatic ring hydrogen), 7.73-7.74 (m, 4h, aromatic ring hydrogen).
The synthesis of embodiment 69- ethoxymethyl-fluorenes formic acid-(9)-methyl ester
With embodiment 1, difference is that the chloromethyl methyl ether in step c is changed to chloromethyl ether to synthesis step.1h- nmr(cdcl3) δ (ppm): 1.11-1.18 (t, 3h, ether methyl hydrogen), 3.40-3.46 (m, 2h, ether methylene hydrogen), 3.66 (s, 3h, METH hydrogen), 3.65-3.79 (s, 2h, ether methylene hydrogen), 7.31-7.34 (t, 2h, aromatic ring hydrogen), 7.40-7.44 (t, 2h, aromatic ring hydrogen), 7.70-7.74 (m, 4h, aromatic ring hydrogen).
The synthesis of embodiment 79- ethoxymethyl-fluorenes formic acid-(9)-ethyl ester
With embodiment 1, difference is that the methanol in step b is changed to ethanol to synthesis step, and by the chloromethane in step c Base methyl ether is changed to chloromethyl ether.1h-nmr(cdcl3) δ (ppm): 1.13-1.17 (t, 3h, ether methyl hydrogen), 1.30-1.34 (t, 3h, METH hydrogen), 3.40-3.46 (m, 2h, ether methylene hydrogen), 3.90 (s, 2h, ether methylene hydrogen), 4.12-4.16 (m, 2h, Ester methylene hydrogen), 7.26-7.40 (t, 2h, aromatic ring hydrogen), 7.41-7.43 (t, 2h, aromatic ring hydrogen), 7.72-7.74 (m, 4h, aromatic ring Hydrogen).
Embodiment 81- benzyloxymethyl -1- methoxy acyl group -2, the synthesis of 5- cyclopentadiene
With step c of embodiment 1, difference is that the chloromethyl methyl ether in step c is changed to chloromethyl benzyl to synthesis step Ether, and 9- methyl formate fluorenes is changed to hexamethylene -2,5- diene-methyl formate.1h-nmr(cdcl3) δ (ppm): 2.62-2.64 (m, 1h, cyclohexadiene hydrogen), 3.63-3.67 (s, 3h, METH hydrogen), 3.77-3.79 (s, 2h, ether methylene hydrogen), 4.60-4.66 (s, 2h, ether methylene hydrogen), 3.90 (s, 2h, ether methylene hydrogen), 5.58-5.62 (d, 2h, cyclohexadiene hydrogen), 5.64-5.70 (m, 2h, cyclohexadiene hydrogen), 7.16-7.20 (m, 5h, aromatic ring hydrogen).
The preparation of ingredient of solid catalyst
The operation preparing catalyst in embodiment is all carried out under high pure nitrogen protection.Specific embodiment is as follows.
Embodiment 9
In 5 mouthfuls of flasks with stirring that 500ml is sufficiently displaced from through nitrogen, add 10g diethoxy magnesium and 80ml first Benzene prepares suspension, is maintained at -15 DEG C of Deca titanium tetrachloride 20ml, after completion of dropping, system is to slowly warm up to after 10 DEG C Deca titanium tetrachloride 60ml, is to slowly warm up to 80 DEG C afterwards again, adds 2.8g9- methoxyl methyl-fluorenes formic acid-(9)-methyl ester, then It is continuously heating to 120 DEG C of constant temperature 2 hours, then that liquid filter pressing is clean, filter off liquid, solid 120ml tetra- chlorination of gained Titanium washs 3 times at 125 DEG C.The solid of gained is washed 2 times at 60 DEG C with 150ml hexane, room temperature washing 2 times, filters off liquid and does Dry, obtain 10.43g pressed powder and be ingredient of solid catalyst, analysis Ti content is 3.90 (wt) %, fluorenes ether-ether content is 16.27 (wt) %.
Embodiment 10
In 5 mouthfuls of flasks with stirring that 500ml is sufficiently displaced from through nitrogen, add 10gmgcl2·2.5c2h5Oh microsphere Prepare suspension with 150ml titanium tetrachloride, be maintained at -15 DEG C 1 hour, be slowly warmed up to 80 DEG C, add 1.5g9- methoxy Methyl-fluorenes formic acid-(9)-methyl ester, then proceedes to be warming up to 110 DEG C of constant temperature 1 hour, then that liquid filter pressing is clean, filters off liquid Body, the solid of gained is washed 3 times at 125 DEG C with 120ml titanium tetrachloride.The solid of gained washs 4 with 150ml hexane at 60 DEG C Secondary, filter off liquid and be dried, obtain 5.61g pressed powder and be ingredient of solid catalyst, analysis Ti content is 3.23 (wt) %, Fluorenes ether-ether content is 23.7 (wt) %.
Embodiment 11
The 2-Ethylhexyl Alcohol of anhydrous magnesium chloride 7.1g, 38ml decane and 35ml reacts 2 hours to be formed uniformly at 130 DEG C Solution.1.7g phthalic anhydride is added, mixture stirs 1 hour at 130 DEG C, so that phthalic anhydride is complete in solution It is dissolved in homogeneous solution.The homogeneous solution obtaining is cooled to room temperature, and is added drop-wise to the 200ml being maintained at -20 DEG C in 1 hour In titanium tetrachloride；Drip rear mixed solution and be heated to 110 DEG C in 4 hours, add 5g9- methoxy when temperature reaches 110 DEG C Methyl-fluorenes formic acid-(9)-methyl ester, mixture stirs 2 hours at the temperature disclosed above.After reaction 2 hours, collected solid by heat filtering Body portion.Solid portion is suspended in 275ml titanium tetrachloride, reacts 2 hours under the conditions of 110 DEG C.After reaction, by heat filtering Collect solids portion, fully washed with decane and hexane at 110 DEG C, after draining, obtain ingredient of solid catalyst, analysis Ti content is 2.6 (wt) %, and fluorenes ether-ether content is 14.6 (wt) %..
Embodiment 12
In 5 mouthfuls of flasks with stirring that 500ml is sufficiently displaced from through nitrogen, room temperature addition 10g anhydrous magnesium chloride, 150ml toluene, 17ml epoxychloropropane and 16ml tributyl phosphate, are warming up to 50 DEG C under stirring, and maintain 2 hours, and solid is complete CL, is subsequently adding 2.40g phthalic anhydride, then maintains 1 hour.Solution is cooled to -25 DEG C, Deca in 1 hour Titanium tetrachloride 110ml, is to slowly warm up to 80 DEG C, in temperature-rise period, progressively washes out solidss.Add 5g9- methoxyl methyl-fluorenes Formic acid-(9)-methyl ester, maintains 1 hour at 80 DEG C.After filtration, 200ml toluene washes twice, be subsequently adding 120ml toluene and 80ml titanium tetrachloride, continues to be warmed up to 110 DEG C, constant temperature 2 hours, then that liquid filter pressing is clean, repeats process once.Filter off Liquid, the solid of gained is washed 1 time with 100ml dichloroethanes, and hexane washs 4 times, obtains 10.2g pressed powder and be after being dried Ingredient of solid catalyst, analysis Ti content is 5.16 (wt) %, and fluorenes ether-ether content is 17.46 (wt) %.Embodiment 13-19
With embodiment 9, difference is to divide 9- methoxyl methyl-fluorenes formic acid-(9)-methyl ester to catalytic component preparation process It is not changed to 9- methoxyl methyl-fluorenes formic acid-(9)-N-butyl, 9- methoxyl methyl-fluorenes formic acid-(9)-isobutyl ester, 9- methoxyl methyl-fluorenes Formic acid-(9)-isopropyl ester, 9- methoxyl methyl-fluorenes formic acid-(9)-ethyl ester, 9- ethoxymethyl-fluorenes formic acid-(9)-methyl ester, 9- ethoxy Methyl-fluorenes formic acid-(9)-ethyl ester or 1- benzyloxymethyl -1- methoxy acyl group -2,5- cyclopentadiene.
Embodiment 20-26
With embodiment 10, difference is to divide 9- methoxyl methyl-fluorenes formic acid-(9)-methyl ester to catalytic component preparation process It is not changed to 9- methoxyl methyl-fluorenes formic acid-(9)-N-butyl, 9- methoxyl methyl-fluorenes formic acid-(9)-isobutyl ester, 9- methoxyl methyl-fluorenes Formic acid-(9)-isopropyl ester, 9- methoxyl methyl-fluorenes formic acid-(9)-ethyl ester, 9- ethoxymethyl-fluorenes formic acid-(9)-methyl ester, 9- ethoxy Methyl-fluorenes formic acid-(9)-ethyl ester or 1- benzyloxymethyl -1- methoxy acyl group -2,5- cyclopentadiene.
Embodiment 27-28
With embodiment 11, difference is to divide 9- methoxyl methyl-fluorenes formic acid-(9)-methyl ester to catalytic component preparation process It is not changed to 9- methoxyl methyl-fluorenes formic acid-(9)-N-butyl or 9- methoxyl methyl-fluorenes formic acid-(9)-ethyl ester.
Polymerization
To carry out polymerization evaluation using solid catalyst as the component of olefin polymerization catalysis:
After 5l stainless steel cauldron is sufficiently displaced from through nitrogen, add the triethyl aluminum hexane that 5ml concentration is 0.5mol/l Solution and 1ml concentration are Cyclohexylmethyldimethoxysilane (cmms) hexane solution of 0.1mol/l and the catalyst of preparation 10mg, is subsequently adding 10ml hexane and rinses charge line, add 2l (under standard state) hydrogen, and 2.5l refines propylene, control System reaction, in 20 DEG C of pre-polymerizations 5 minutes, is warming up to 70 DEG C, at this temperature polyreaction 1 hour.After reaction terminates, by reactor Lower the temperature and stop stirring and discharge product, drying obtains polymer.(bulk density of polymer adopts jb/t2412-2008 Method, isotacticity adopts jb/t3682-2000 method.)
Table 1 catalyst performance
Upper table polymerization result shows, using the fluorenes ether acid ester selected from ring replacement ether acid ester compounds as internal electron donor, Using the catalyst obtained by four kinds of different catalyst preparation process, the work of higher level during for propylene polymerization, can be obtained Property, and under standard polymerization conditions, the polypropylene prepared by cooperation Cyclohexylmethyldimethoxysilane external electron donor has It is substantially higher than 97% isotacticity, illustrate that such compound can be applied to various typical catalyst preparations as internal electron donor Route, and make catalyst play outstanding polymerization, obtain the polypropylene product of higher catalysis activity and high isotactic.
Although, above the present invention is described in detail with a general description of the specific embodiments, On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause This, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to the scope of protection of present invention.

Claims (13)

1. it is used for the ingredient of solid catalyst of olefinic polymerization it is characterised in that it comprises mg, ti, halogen and a kind of electron donor, This electron donor is selected from least one ring replacement ether acid ester compounds of following formulas ():
Wherein, r1And r4For c that is identical or differing1-c20Straight or branched alkyl, alkenyl, c3-c20Cycloalkyl, c6-c20Virtue Base, c7-c20Alkaryl and c7-c20Aralkyl；Identical or different r2、r3It is c1-c20Straight or branched alkyl, c3-c20Cycloalkanes Base, c6-c20Aryl, c7-c20Alkaryl and c7-c20Aralkyl；
Above-mentioned r1-r4Arbitrarily comprise one or several r atoms as carbon atom or hydrogen atom or both substituents, r atom It is hetero atom, the c of straight or branched1-c20Alkyl, c3-c20Cycloalkyl, c6-c20Aryl, c7-c20Alkaryl and c7-c20Aralkyl Base；Wherein r1-r4Any two group can be mutually bonded the one or more volutions of generation, condensed cyclic structure；R ' is identical or not phase Hydrogen together, halogen atom, the c of straight or branched1-c20Alkyl, c3-c20Cycloalkyl, c6-c20Aryl, c7-c20Alkaryl and c7-c20 Aralkyl.
2. the ingredient of solid catalyst for olefinic polymerization according to claim 1 is it is characterised in that described compound The group constituting selected from following compounds:
9- methoxyl methyl-fluorenes formic acid-(9)-methyl ester；9- ethoxymethyl-fluorenes formic acid-(9)-methyl ester；9- methoxyl methyl-fluorenes formic acid- (9)-ethyl ester；9- methoxyl methyl-fluorenes formic acid-(9)-N-butyl；9- methoxyl methyl-fluorenes formic acid-(9)-isobutyl ester；9- methoxy first Base-fluorenes formic acid-(9)-isopropyl ester；9- ethoxymethyl-fluorenes formic acid-(9)-ethyl ester；9- ethoxymethyl-fluorenes formic acid-(9)-N-butyl； 9- ethoxymethyl-fluorenes formic acid-(9)-isobutyl ester；9- ethoxymethyl-fluorenes formic acid-(9)-isopropyl ester；1- benzyloxymethyl -1- methoxy acyl Base -2,5- cyclopentadiene.
3. ingredient of solid catalyst according to claim 1 and 2 it is characterised in that comprise titanium compound, magnesium compound and Replace the product of ether acid ester compounds selected from the ring of described formula (), the precursor of described magnesium compound is selected from least one Kind: mg (or)2, xnmg(or)2-n, mgcl2Mroh, r2-nmgxn, mgr2, mgcl2/sio2, mgcl2/al2o3, or magnesium halide and The mixture of alcohol titanium, in formula, m is the number of 0.1-6, and 0 < n < 2, x is halogen, and r is hydrogen or c1-c20Alkyl；Described titanium compound Formula is tixn(or)4-n, in formula, r is the alkyl of 1-20 for carbon number, and x is halogen, n=1-4.
4. a kind of method of the ingredient of solid catalyst for olefinic polymerization preparing claim 3 is it is characterised in that include: Make magnesium compound replace ether acid ester internal electron donor compound with titanium compound with the ring selected from described formula () to contact, thus Obtain ingredient of solid catalyst.
5. the preparation method of the ingredient of solid catalyst for olefinic polymerization according to claim 4 is it is characterised in that institute State magnesium compound by wherein at least one halogen atom in magnesium dihalide molecular formula by spreading out that oxyl or halo oxyl are replaced One of biology；Or described magnesium compound is alkoxyl magnesium or aryloxy group magnesium；Or described magnesium compound is the alcohol of magnesium dihalide Compound；Or described magnesium compound is to make to lead in the presence of a kind of compound selected from alcohol, phenol, ketone, aldehyde, ether, amine, pyridine and ester Formula r2-nmgxnLiquid magnesium compound contact with liquid titanium compound reprecipitation separate out solid.
6. one kind is used for alkene ch2The catalyst of=chr polymerization, wherein r is hydrogen or the hydrocarbyl group containing 1-12 carbon atom, its It is characterised by, including the product of following substance reaction:
Ingredient of solid catalyst any one of (a) claim 1-3；
B () at least one formula is alrnx(3-n)Organo-aluminum compound, in formula r be hydrogen, the alkyl of carbon number 1-20；X is Halogen, n is the integer of 0≤n≤3；With, optionally,
(c) at least one external donor compound.
7. catalyst according to claim 6 is it is characterised in that organo-aluminum compound (b) is a kind of trialkylaluminium chemical combination Thing.
8. catalyst according to claim 7 is it is characterised in that trialkyl aluminium compound is selected from trimethyl aluminium, triethyl group Aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, trioctylaluminum.
9. catalyst according to claim 6 is it is characterised in that it is r that described external electron donor (c) is selected from formulansi (or1)4-nSilicone compounds, r and r in formula1For c1-c18Alkyl, optionally also hetero atom；N is the integer of 0≤n≤3.
10. one kind is used for alkene ch2The pre-polymerized catalyst of=chr polymerization, wherein r is hydrogen or the alkyl containing 1-12 carbon atom Group it is characterised in that described pre-polymerized catalyst comprise a kind of according to the solid catalysis any one of claim 1-3 Agent component and alkene carry out the prepolymer of prepolymerization gained.
11. pre-polymerized catalysts according to claim 10 are it is characterised in that carrying out prepolymerized alkene is ethylene or third Alkene.
12. are used for alkene ch2The method of=chr polymerization, including homopolymerization, pre-polymerization and copolymerization, wherein r is hydrogen or former containing 1-12 carbon The hydrocarbyl group of son, is carried out in the presence of the catalyst any one of in claim 6-11 or pre-polymerized catalyst.
13. methods according to claim 12 are it is characterised in that alkene is selected from ethylene, propylene, 1-butylene, 1- amylene, 1- Hexene, 4-methyl-1-pentene, 1- heptene, 1- nonene, 1-decene；Branched-chain alkene is: 3-methyl-1-butene and 4- methyl-1-pentene Alkene；Alkadienes are: butadiene, vinylcyclopentene and VCH.
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